Hydrogen absorbing alloy electrode, method of fabricating hydrogen absorbing alloy electrode, and alkali secondary battery

ABSTRACT

In the present invention, a hydrogen absorbing alloy containing at least nickel, cobalt and aluminum, in which the sum a of the respective abundance ratios of cobalt atoms and aluminum atoms in a portion to a depth of 30 Å from its surface and the sum b of the respective abundance ratios of cobalt atoms and aluminum atoms in a bulk region inside thereof satisfy conditions of a/b≧1.30, or a hydrogen absorbing alloy containing at least nickel, cobalt, aluminum and manganese, in which the sum A of the respective abundance ratios of cobalt atoms, aluminum atoms and manganese atoms in a portion to a depth of 30 Å from its surface and the sum B of the respective abundance ratios of cobalt atoms, aluminum atoms and manganese atoms in a bulk region inside thereof satisfy conditions A/B≧1.20 is used for a hydrogen absorbing alloy electrode in an alkali secondary battery.

This application is a division of prior application Ser. No. 08/978,271filed Nov. 25, 1997, now U.S. Pat. No. 5,985,057.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a hydrogen absorbing alloy electrodeused as a negative electrode of an alkali secondary battery such as anickel-hydrogen secondary battery, a method of fabricating the hydrogenabsorbing alloy electrode, and an alkali secondary battery using thehydrogen absorbing alloy electrode, and is characterized in that ahydrogen absorbing alloy used for the hydrogen absorbing alloy electrodeis modified, to improve the activity in the early stages of the hydrogenabsorbing alloy electrode and the characteristics thereof at lowtemperature.

2. Description of the Related Art

A nickel-hydrogen secondary battery has been conventionally known as oneexample of an alkali secondary battery. In the nickel-hydrogen secondarybattery, a hydrogen absorbing alloy electrode using a hydrogen absorbingalloy has been generally used as its negative electrode.

Examples of the hydrogen absorbing alloy used for the negative electrodeinclude a hydrogen absorbing alloy having a CaCu₅-type crystal structureusing Misch metal (Mm) which is a mixture of rare earth elements or aLaves type hydrogen absorbing alloy.

In each of the hydrogen absorbing alloys, however, a coating of an oxideor the like is generally formed on its surface by natural oxidation, forexample. When a hydrogen absorbing alloy electrode is fabricated usingsuch a hydrogen absorbing alloy, and the hydrogen absorbing alloyelectrode is used as a negative electrode of the nickel-hydrogensecondary battery, the activity in the early stages of the hydrogenabsorbing alloy is low, and hydrogen gas is not sufficiently absorbed inthe hydrogen absorbing alloy. As a result, some problems arise. Forexample, the capacity in the early stages of the nickel-hydrogensecondary battery is decreased, and the internal pressure of the batteryis increased by the hydrogen gas.

Therefore, in recent years, a method of immersing a hydrogen absorbingalloy in an acid solution such as hydrochloric acid, to remove a coatingof an oxide on the surface of the hydrogen absorbing alloy has beenproposed, as disclosed in Japanese Patent Laid-Open No. 225975/1993.

When the hydrogen absorbing alloy is thus immersed in the acid solution,to remove the coating of the oxide on the surface of the hydrogenabsorbing alloy, some active portions appear on the surface of thehydrogen absorbing alloy.

However, the active portions thus appearing on the surface are oxidizedagain, whereby the activity in the early stages of the hydrogenabsorbing alloy is not sufficiently improved, and the hydrogen gas isnot sufficiently absorbed in the hydrogen absorbing alloy in the earlystages. As a result, some problems still exist. For example, thecapacity in the early stages of the battery is low, and the internalpressure of the battery is increased.

Furthermore, in the hydrogen absorbing alloy electrode using theconventional hydrogen absorbing alloy, the electrochemical catalyticcapability thereof is not sufficient, resulting in inferior dischargecharacteristics in a case where it is used under low temperature.

SUMMARY OF THE INVENTION

An object of the present invention is to improve, in a hydrogenabsorbing alloy electrode used as a negative electrode of an alkalisecondary battery such as a nickel-hydrogen secondary battery, theactivity in the early stages of the hydrogen absorbing alloy electrodewhich is used as the negative electrode.

Another object of the present invention is to simply obtain a hydrogenabsorbing alloy electrode whose activity in the early stages isimproved, resulting in increased charging and dischargingcharacteristics.

Still another object of the present invention is to improve, in analkali secondary battery using a hydrogen absorbing alloy electrode asits negative electrode, the discharge capacity thereof in the earlystages and prevent the internal pressure of the battery from beingincreased.

A further object of the present invention is to obtain, in an alkalisecondary battery using a hydrogen absorbing alloy electrode as itsnegative electrode, sufficient discharge characteristics even in a casewhere the battery is used under low temperature.

In a first hydrogen absorbing alloy electrode according to the presentinvention, a hydrogen absorbing alloy containing at least nickel, cobaltand aluminum is used. Letting a be the sum of the respective abundanceratios of cobalt atoms and aluminum atoms in a portion to a depth of 30Å from the surface of the hydrogen absorbing alloy, and b be the sum ofthe respective abundance ratios of cobalt atoms and aluminum atoms in abulk region inside the hydrogen absorbing alloy, conditions of a/b≧1.30are satisfied.

As in the first hydrogen absorbing alloy electrode, when more cobaltatoms and aluminum atoms exist on the surface of the hydrogen absorbingalloy, as compared with those in the bulk region inside the hydrogenabsorbing alloy, the catalytic actions of the cobalt atoms and thealuminum atoms cause the activity of the hydrogen absorbing alloyelectrode using the hydrogen absorbing alloy to be improved from theearly stages and cause the electron conductivity thereof under lowtemperature to be improved.

When the first hydrogen absorbing alloy electrode is used as a negativeelectrode of an alkali secondary battery such as a nickel-hydrogensecondary battery, the emission of hydrogen gas in the early stages isrestrained, so that the capacity in the early stages of the battery isincreased, and the internal pressure of the battery is prevented frombeing increased. Further, the electrochemical catalytic capability ofthe hydrogen absorbing alloy electrode is improved.

In a second hydrogen absorbing alloy electrode according to the presentinvention, a hydrogen absorbing alloy containing at least nickel,cobalt, aluminum and manganese is used. Letting A be the sum of therespective abundance ratios of cobalt atoms, aluminum atoms andmanganese atoms in a portion to a depth of 30 Å from the surface of thehydrogen absorbing alloy, and B be the sum of the respective abundanceratios of cobalt atoms, aluminum atoms and manganese atoms in a bulkregion inside the hydrogen absorbing alloy, conditions of A/B≧1.20 aresatisfied.

As in the second hydrogen absorbing alloy electrode, when more cobaltatoms, aluminum atoms and manganese atoms exist on the surface of thehydrogen absorbing alloy, as compared with those in the bulk regioninside the hydrogen absorbing alloy, the catalytic actions of the cobaltatoms, the aluminum atoms and the manganese atoms cause the activity ofthe hydrogen absorbing alloy electrode using the hydrogen absorbingalloy to be improved from the early stages and cause the electrochemicalcatalytic capability thereof to be improved.

When the second hydrogen absorbing alloy electrode is used as a negativeelectrode of an alkali secondary battery such as a nickel-hydrogensecondary battery, the emission of hydrogen gas in the early stages isrestrained, so that the capacity in the early stages of the battery isincreased, and the internal pressure of the battery is prevented frombeing increased. Further, the discharge characteristics in a case wherethe battery is used under low temperature are also improved.

In a first method of fabricating a hydrogen absorbing alloy electrodeaccording to the present invention, in fabricating a hydrogen absorbingalloy electrode using a hydrogen absorbing alloy containing at leastnickel, cobalt and aluminum, the hydrogen absorbing alloy issurface-treated in an acid solution to which 1 to 5% by weight of acobalt compound and an aluminum compound per the weight of the hydrogenabsorbing alloy are respectively added.

When the hydrogen absorbing alloy containing nickel, cobalt and aluminumis thus surface-treated in the acid solution to which the cobaltcompound and the aluminum compound are added, active portions appear onthe surface of the hydrogen absorbing alloy, and the active portions areprotected by a protective film composed of CoAl₂O₄. Therefore, theactive portions are prevented from being oxidized again, and therespective numbers of the cobalt atoms and the aluminum atoms on thesurface of the hydrogen absorbing alloy are larger than those in thebulk region inside the hydrogen absorbing alloy.

When the amounts of cobalt compound and the aluminum compound which areadded to the acid solution are respectively set in the range of 1 to 5%by weight per the weight of the hydrogen absorbing alloy, theabove-mentioned first hydrogen absorbing alloy electrode in which therelationship between the sum a of the respective abundance ratios ofcobalt atoms and aluminum atoms in the portion to a depth of 30 Å fromthe surface of the hydrogen absorbing alloy and the sum b of therespective abundance ratios of cobalt atoms and aluminum atoms in thebulk region inside the hydrogen absorbing alloy satisfies conditions ofa/b≧1.30 is obtained.

When the respective amounts of the cobalt compound and the aluminumcompound which are added to the acid solution are less than theabove-mentioned range, the respective numbers of the cobalt atoms andthe aluminum atoms in the portion to a depth of 30 Å from the surface ofthe hydrogen absorbing alloy are decreased. On the other hand, if therespective amounts of the cobalt compound and the aluminum compound aretoo large, the cobalt atoms and the aluminum atoms do not remain on thesurface of the hydrogen absorbing alloy. In either one of the cases, thehydrogen absorbing alloy electrode satisfying the conditions of a/b≧1.30is not obtained.

As the cobalt compound and the aluminum compound which are added to theacid solution, any compounds which can be dissolved in the acid solutionmay be used. Examples of the cobalt compound include cobalt chloride andcobalt hydroxide (including cobalt oxyhydroxide). Examples of thealuminum compound include aluminum chloride and aluminum hydroxide.

In a second method of fabricating a hydrogen absorbing alloy electrodeaccording to the present invention, in fabricating a hydrogen absorbingalloy electrode using a hydrogen absorbing alloy containing at leastnickel, cobalt, aluminum and manganese, the hydrogen absorbing alloy issurface-treated in an acid solution to which 1 to 5% by weight of analuminum compound per the weight of the hydrogen absorbing alloy isadded.

When the hydrogen absorbing alloy containing nickel, cobalt, aluminumand manganese is thus surface-treated in the acid solution to which thealuminum compound is added, the respective numbers of the cobalt atomsand the aluminum atoms on the surface of the hydrogen absorbing alloyare larger than those in the bulk region inside the hydrogen absorbingalloy.

When the amount of the aluminum compound added to the acid solution isset in the range of 1 to 5% by weight per the weight of the hydrogenabsorbing alloy, the above-mentioned second hydrogen absorbing alloyelectrode in which the relationship between the sum A of the respectiveabundance ratios of cobalt atoms, aluminum atoms and manganese atoms inthe portion to a depth of 30 Å from the surface of the hydrogenabsorbing alloy and the sum B of the respective abundance ratios ofcobalt atoms, aluminum atoms and the manganese atoms in the bulk regioninside the hydrogen absorbing alloy satisfies conditions of A/B≧1.20 isobtained.

When the amount of the aluminum compound added to the acid solution isless than the above-mentioned range, the respective numbers of thecobalt atoms, the aluminum atoms and the manganese atoms in the portionto a depth of 30 Å from the surface of the hydrogen absorbing alloy aredecreased. On the other hand, if the amount of the aluminum compound istoo large, the cobalt atoms, the aluminum atoms and the manganese atomsdo not remain on the surface of the hydrogen absorbing alloy. In eitherone of the cases, the hydrogen absorbing alloy electrode satisfying theconditions of A/B≧1.20 and a/b≧1.3 is not obtained.

In each of the first and second methods of fabricating the hydrogenabsorbing alloy electrode, if the pH of the acid solution is too high, acoating of an oxide or the like on the surface of the hydrogen absorbingalloy cannot be sufficiently removed. On the other hand, if the pH ofthe acid solution is too low, an active metal in the hydrogen absorbingalloy is dissolved, so that the number of active portions on the surfaceof the hydrogen absorbing alloy is decreased. Therefore, the initial pHof the acid solution is set preferably in the range of 0.7 to 2.0.

When the temperature of the acid solution is too high, the active metalin the hydrogen absorbing alloy is also dissolved, so that the number ofthe active portions on the surface of the hydrogen absorbing alloy isdecreased. On the other hand, if the temperature of the acid solution istoo low, the coating of the oxide or the like on the surface of thehydrogen absorbing alloy cannot be sufficiently removed. Therefore, thetemperature of the acid solution is set preferably in the range of 20°C. to 70° C.

Furthermore, in treating the hydrogen absorbing alloy in the acidsolution as described above, it is preferable that a quinone compoundsuch as anthrahydroquinone is added to the acid solution. When thequinone compound is thus added to the acid solution, dissolved oxygen inthe acid solution is removed, so that the active portions appearing onthe surface of the hydrogen absorbing alloy are prevented from beingoxidized again, and the activity in the early stages of the hydrogenabsorbing alloy is further improved. The amount of the quinone compoundadded to the acid solution is preferably 5 ppm to 100 ppm.

The hydrogen absorbing alloy having a CaCu₅-type crystal structure usedin the present invention is represented by a general formulaMmNi_(a)Co_(b)Al_(c)Mn_(d). In the formula, Mm is a mixture of rareearth elements selected from La, Ce, Pr, Nd, Sm, Eu, Sc, Y, Pm, Gd, Tb,Gy, Ho, Er, Tm, Yb and Lu. Particularly, Mm mainly composed of a mixtureof La, Ce, Pr, Nd and Sm is preferable. Further, a>0, b>0, c>0, and d≧0,and 4.4≦a+b+c+d≦5.4.

The hydrogen absorbing alloy composed of the above-mentioned compositioncan satisfy the basic performance such as cycle characteristics anddischarge characteristics of the alkali secondary battery. Further,elements Si, C, W and B may be added in the range in which theproperties of absorbing hydrogen in the hydrogen absorbing alloy are notchanged.

In the above-mentioned composition formula, it is preferable that theamount a of nickel is 2.8≦a≦5.2, the amount b of cobalt is 0<b≦1.4, theamount c of aluminum is 0<c≦1.2, and the amount d of manganese is d≦1.2.Further, in order to increase the capacity of the battery, it ispreferable that the amount c of aluminum is c≦1.0, and the amount d ofmanganese is d≦1.0.

There and other objects, advantages and features of the invention willbecome apparent from the following description thereof taken inconjunction with the accompanying drawings which illustrate specificembodiment of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view of a nickel-hydrogen secondarybattery fabricated in embodiments and comparative examples of thepresent invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A hydrogen absorbing alloy electrode, a method of fabricating thehydrogen absorbing alloy electrode, and an alkali secondary batteryaccording to embodiments of the present invention will be specificallydescribed, and comparative examples will be taken, to make it clear thatin an alkali secondary battery using a hydrogen absorbing alloyelectrode in the present embodiments as its negative electrode, theinternal pressure in the early stages of the battery is prevented frombeing increased, and the discharge characteristics thereof under lowtemperature are improved. The hydrogen absorbing alloy electrode, themethod of fabricating the hydrogen absorbing alloy electrode, and thealkali secondary battery in the present invention are not particularlylimited to those in the following embodiments, and can be embodied uponbeing suitably changed in the range in which the gist thereof is notchanged.

(Embodiments 1 to 3 and Comparative Examples 1 to 3)

In the embodiments 1 to 3 and the comparative examples 1 to 3, Mischmetal (Mm) which is a mixture of rare earth elements, Ni, Co, Al and Mnwere so weighed and mixed as to have a composition ofMmNi_(3.1)Co_(0.8)Al_(0.4)Mn_(0.7), were fussed and alloyed, and werethen mechanically ground, to obtain hydrogen absorbing allow powder.

The surface of the hydrogen absorbing alloy powder thus obtained wastreated in an acid solution using hydrochloric acid.

In thus treating the surface of the hydrogen absorbing alloy powder inthe acid solution, the initial pH of the acid solution was set to 1.0,and the liquid temperature thereof was set to 25° C., as shown in thefollowing Table 1. Further, in the embodiments 1 to 3 and thecomparative example 1, aluminum chloride (AlCl₃) and cobalt chloride(CoCl₂) were respectively added as an aluminum compound and a cobaltcompound to the acid solution in proportions shown in the same table,and 50 ppm of anthraquinone was added. In the comparative example 2, 50ppm of only anthraquinone was added. In the comparative example 3, noneof aluminum chloride, cobalt chloride and anthraquinone was added.

A hydrogen absorbing alloy was immersed in each of the acid solutionsadjusted in the above-mentioned manner until the pH thereof would be7.0, to treat the surface of the hydrogen absorbing alloy.

The abundance ratio of each type of atoms in a portion to a depth of 30Å from the surface of each of the hydrogen absorbing alloyssurface-treated in the above-mentioned manner was then measured. Theabundance ratio of the atoms was measured using a scanning transmissionelectron micro scope and a transmission electron micro scope and by anenergy dispersion type X-ray analysis method. The abundance ratio of theatoms means the ratio of the number of the atoms to the total number ofall metallic atoms detected by the energy dispersion type X-ray analysismethod.

By this method, the sum a of the respective abundance ratios of Co atomsand Al atoms in the portion to a depth of 30 Å from the surface of eachof the hydrogen absorbing alloys was found, and the sum b of therespective abundance ratios of Co atoms and Al atoms in a bulk regioninside the hydrogen absorbing alloy was similarly found, to calculatea/b. The results thereof were together shown in the following Table 1.

TABLE 1 embodiment comparative example 1 2 3 1 2 3 treating conditionsof acid solution pH 1.0 1.0 1.0 1.0 1.0 1.0 liquid temperature 25 25 2525 25 25 (° C.) AlCl₃ (% by weight) 1 3 5 7 0 0 CoCl₂ (% by weight) 1 35 7 0 0 anthraquinone (ppm) 50 50 50 50 50 0 abundance ratio of atoms onsurface Co (atm/%) 19.45 21.22 22.34 19.45 15.56 15.56 Al (atm/%) 2.893.04 3.34 2.34 1.20 1.20 a (atm/%) 22.34 24.26 25.68 21.79 16.76 16.76abundance ratio of atoms inside b (atm/%) 17.21 17.76 18.02 17.82 17.0117.01 a/b 1.30 1.37 1.43 1.22 0.99 0.99

As a result, in the hydrogen absorbing alloys in the embodiments 1 to 3,the value of a/b was not less than 1.30, which satisfied the conditionsof the present invention. On the other hand, in the hydrogen absorbingalloy in the comparative example 1 which was treated using an acidsolution to which 7% by weight, which is more than 5% by weight, ofAlCl₃ and CoCl₂ were added, and the hydrogen absorbing alloy in each ofthe comparative examples 2 and 3 which was treated using an acidsolution to which no AlCl₃ and CoCl₂ were added, the value of a/b wasless than 1.30.

20 parts by weight of a 5% solution of polyethylene oxide which is abinder was then added and mixed with 100 parts by weight of each of thehydrogen absorbing alloys surface-treated as shown in the embodiments 1to 3 and the comparative examples 1 and 2, and paste was prepared, wasapplied to both surfaces of a conductive substrate composed of a punchedmetal nickel-plated and was dried at room temperature, and was then cutto predetermined lengths, to fabricate each of hydrogen absorbing alloyelectrodes in the embodiments 1 to 3 and the comparative examples 1 and2.

Each of the hydrogen absorbing alloy electrodes thus fabricated was usedas a negative electrode, while a sintered type nickel electrodeconventionally used was used as a positive electrode. Further, anon-woven fabric having alkali resistance was used as a separator.

As shown in FIG. 1, a separator 3 was interposed between the positiveelectrode 1 and each of the negative electrodes 2, and they werecontained in a battery can 4 upon being spirally wound, after which 30%by weight of a potassium hydroxide solution was pored as an alkalielectrolyte into the battery can 4, the battery can 4 was sealed, thepositive electrode 1 was connected to a positive electrode cover 6through a positive electrode lead 5, and the negative electrode 2 wasconnected to the battery can 4 through a negative electrode lead 7, toelectrically separate the battery can 4 and the positive electrode cover6 by an insulating packing 8.

A coil spring 10 was provided between the positive electrode cover 6 anda positive electrode external terminal 9. When the internal pressure ofthe battery was abnormally increased, the coil spring 10 was compressed,so that gas inside the battery was discharged into the air.

Each of the above-mentioned nickel-hydrogen secondary batteries was sodesigned that the discharge capacity thereof would be 1000 mAh at atemperature of 25° C. and at a current of 0.2 C.

Each of the nickel-hydrogen secondary batteries fabricated in theabove-mentioned manner was charged at a charging current of 0.2 C forsix hours under room temperature (ordinary temperature), and was thendischarged at a discharging current of 0.2 C under low temperature of 0°C., to find the initial discharge capacity of the nickel-hydrogensecondary battery. The results thereof were shown in the following Table2.

TABLE 2 type of hydrogen absorbing initial discharge capacity alloyelectrode (mAh) embodiment 1 666 embodiment 2 669 embodiment 3 687comparative example 1 465 comparative example 2 445

As apparent from the results, in each of the nickel-hydrogen secondarybatteries respectively using as their negative electrodes the hydrogenabsorbing alloy electrodes in the embodiments 1 to 3 using the hydrogenabsorbing alloys in which the value of a/b was not less than 1.30, theinitial discharge capacity thereof in a case where it was used under lowtemperature of 0° C. was higher, and the discharge characteristicsthereof under low temperature are improved, as compared with those ineach of the nickel-hydrogen secondary batteries using as their negativeelectrodes the hydrogen absorbing alloy electrodes in the comparativeexamples 1 and 2 respectively using the hydrogen absorbing alloys inwhich the value of a/b was less than 1.30.

(Embodiments 4 to 6 and Comparative Examples 4 to 6)

In the embodiments 4 to 6 and the comparative examples 4 to 6, insurface-treating in an acid solution hydrogen absorbing alloys obtainedby grinding in the same manner as described in the embodiments 1 to 3and the comparative examples 1 to 3, the liquid temperature of the acidsolution was set to 25° C., and the amounts of AlCl₃, CoCl₂ andanthraquinone which were added to the acid solution in the embodiment 4were made the same as those in the embodiment 1, the amounts in theembodiment 5 were made the same as those in the embodiment 2, theamounts in the embodiment 6 were made the same as those in theembodiment 3, the amounts in the comparative example 4 were made thesame as those in the comparative example 1, the amounts in thecomparative example 5 were made the same as those in the comparativeexample 2, and the amounts in the comparative example 6 were made thesame as those in the comparative example 3 as shown in the followingTable 3, while the initial pH of the acid solution was changed as shownin the same table, to respectively surface-treat the hydrogen absorbingalloys.

Even when the initial pH of the acid solution was changed as describedabove, the value of a/b was hardly changed, that is, the value in theembodiment 4 was approximately the same as that in the embodiment 1, thevalue in the embodiment 5 was approximately the same as that in theembodiment 2, the value in the embodiment 6 was approximately the sameas that in the embodiment 3, the value in the comparative example 4 wasapproximately the same as that in the comparative example 1, the valuein the comparative example 5 was approximately the same as that in thecomparative example 2, and the value in the comparative example 6 wasapproximately the same as that in the comparative example 3.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 1 to 3 and thecomparative examples 1 and 2 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure of each of the nickel-hydrogen secondary batteriesthus fabricated was measured while charging the battery at a current of1000 mA (1C) under room temperature, to measure a charging time periodelapsed until the internal pressure of the battery reaches 10 kgf/cm².The charging time period was shown as the internal pressurecharacteristics in the early stages of the nickel-hydrogen secondarybattery in the following Table 3. In determining the internal pressurecharacteristics, tests were conducted with respect to fournickel-hydrogen secondary batteries, and the average value thereof wasshown.

TABLE 3 AlCl₃ + internal pressure CoCl₂ anthra- characteristics (min) (%by quinone pH weight) (ppm) 0.5 0.7 1.0 1.5 2.0 3.0 embodiment 1 + 1 50115 140 145 140 135 105 4 embodiment 3 + 3 50 110 140 145 145 135 100 5embodiment 5 + 5 50 105 145 145 145 135 100 6 comparative 7 + 7 50 100125 120 120 110 100 example 4 comparative 0 50 95 115 120 120 110 90example 5 comparative 0 0 95 110 125 120 115 90 example 6

As apparent from the results, even when the initial pH of the acidsolution was changed, the charging time period indicating the internalpressure characteristics of the battery in each of the embodiments 4 to6 in which the value of a/b was not less than 1.30 as in theabove-mentioned embodiments 1 to 3 was longer than that in each of thecomparative examples 4 to 6 in which the value of a/b was less than 1.30as in the comparative examples 1 to 3. Therefore, the emission of gas inthe early stages was restrained, so that a sufficient discharge capacitywas obtained from the early stages.

In surface-treating the hydrogen absorbing alloy in the acid solution asdescribed above, when the hydrogen absorbing alloy was treated in anacid solution whose initial pH was in the range of 0.7 to 2.0, theinternal pressure characteristics of the nickel-hydrogen secondarybattery were further improved.

(Embodiments 7 to 9 and Comparative Examples 7 to 9)

In the embodiments 7 to 9 and the comparative examples 7 to 9, insurface-treating in an acid solution hydrogen absorbing alloys obtainedby grinding in the same manner as described in the embodiments 1 to 3and the comparative examples 1 to 3, the initial pH of the acid solutionwas set to 1.0, and the amounts of AlCl₃, CoCl₂ and anthraquinone whichwere added to the acid solution in the embodiment 7 were made the sameas those in the embodiment 1, the amounts in the embodiment 8 were madethe same as those in the embodiment 2, the amounts in the embodiment 9were made the same as those in the embodiment 3, the amounts in thecomparative example 7 were made the same as those in the comparativeexample 1, the amounts in the comparative example 8 were made the sameas those in the comparative example 2, and the amounts in thecomparative example 9 were made the same as those in the comparativeexample 3 as shown in the following Table 4, while the liquidtemperature of the acid solution was changed as shown in the same table,to respectively surface-treat the hydrogen absorbing alloys.

Even when the liquid temperature of the acid solution was changed asdescribed above, the value of a/b was hardly-changed, that is, the valuein the embodiment 7 was approximately the same as that in the embodiment1, the value in the embodiment 8 was approximately the same as that inthe embodiment 2, the value in the embodiment 9 was approximately thesame as that in the embodiment 3, the value in the comparative example 7was approximately the same as that in the comparative example 1, thevalue in the comparative example 8 was approximately the same as that inthe comparative example 2, and the value in the comparative example 9was approximately the same as that in the comparative example 3.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 1 to 3 and thecomparative examples 1 and 2 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries was measured in the same manner as described above.The results thereof were shown in the following Table 4.

TABLE 4 internal pressure AlCl₃ + characteristics (min) CoCl₂ anthra-liquid temperature of acid (% by quinone solution (° C.) weight) (ppm)10.0 25.0 40.0 60.0 70.0 80.0 embodiment 1 + 1 50 125 140 140 145 140100 7 embodiment 3+3 50 130 145 145 145 140 115 8 embodiment 5 + 5 50130 145 145 145 145 100 9 comparative 7 + 7 50 120 120 135 130 110 100example 7 comparative 0 50 115 120 120 120 110 90 example 8 comparative0 0 120 125 120 120 110 100 example 9

As apparent from the results, when the liquid temperature of the acidsolution was in the range of 25.0° C. to 70.0° C., the charging timeperiod indicating the internal pressure characteristics of the batteryin each of the embodiments 7 to 9 in which the value of a/b was not lessthan 1.30 as described above was longer than that in each of thecomparative examples 7 to 9 in which the value of a/b was less than1.30. Therefore, the emission of gas in the early stages was restrained,so that a sufficient discharge capacity was obtained from the earlystages.

(Embodiments 10 to 12 and Comparative Examples 10 and 11)

In the embodiments 10 to 12 and the comparative examples 10 and 11, insurface-treating in an acid solution hydrogen absorbing alloys obtainedby grinding in the same manner as described in the embodiments 1 to 3and the comparative examples 1 to 3, the initial pH of the acid solutionwas set to 1.0, the liquid temperature thereof was set to 25° C., andthe amounts of AlCl₃ and CoCl₂ which were added to the acid solution inthe embodiment 10 were made the same as those in the embodiment 1, theamounts in the embodiment 11 were made the same as those in theembodiment 2, the amounts in the embodiment 12 were made the same asthose in the embodiment 3, the amounts in the comparative example 10were made the same as those in the comparative example 1, and theamounts in the comparative example 11 were made the same as those in thecomparative example 2 as shown in the following Table 5, while theamount of anthraquinone added to the acid solution was changed as shownin the same table, to respectively surface-treat the hydrogen absorbingalloys.

Even when the amount of anthraquinone added to the acid solution waschanged as described above, the value of a/b was hardly changed, thatis, the value in the embodiment 10 was approximately the same as that inthe embodiment 1, the value in the embodiment 11 was approximately thesame as that in the embodiment 2, the value in the embodiment 12 wasapproximately the same as that in the embodiment 3, the value in thecomparative example 10 was approximately the same as that in thecomparative example 1, and the value in the comparative example 11 wasapproximately the same as that in the comparative example 2.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 1 to 3 and thecomparative examples 1 and 2 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries was measured in the same manner as described above.The results thereof were shown in the following Table 5.

TABLE 5 internal pressure characteristics AlCl₃ + (min) CoCl₂ amount ofadded anthraquinone (% by (ppm) weight) 0.0 5.0 10.0 50.0 100.0 200.0embodiment 1 + 1 125 140 145 145 145 105 10 embodiment 3 + 3 125 140 145145 140 105 11 embodiment 5 + 5 125 145 145 145 145 105 12 comparative7 + 7 125 125 130 120 120 100 example 10 comparative 0 125 110 120 120 90  80 example 11

As apparent from the results, when the amount of anthraquinone added tothe acid solution was in the range of 5.0 ppm to 100.0 ppm, the chargingtime period indicating the internal pressure characteristics of thebattery in each of the embodiments 10 to 12 in which the value of a/bwas not less than 1.30 as described above was longer than that in eachof the comparative examples 10 to 11 in which the value of a/b was lessthan 1.30. Therefore, the emission of gas in the early stages wasrestrained, so that a sufficient discharge capacity was obtained fromthe early stages.

(Embodiments 13 to 15 and Comparative Example 12)

In the embodiments 13 to 15 and the comparative example 12, insurface-treating in an acid solution hydrogen absorbing alloys obtainedby grinding in the same manner as described in the embodiments 1 to 3and the comparative examples 1 to 3, the initial pH of the acid solutionwas set to 1.0, the liquid temperature thereof was set to 25° C., and 50ppm of anthraquinone was added, while aluminum hydroxide {Al(OH)₃} andcobalt chloride (CoCl₂) were respectively added as an aluminum compoundand a cobalt compound to the acid solution in proportions as shown inthe following Table 6.

The abundance ratio of each type of atoms in a portion to a depth of 30Å from the surface of each of the hydrogen absorbing alloyssurface-treated in the above-mentioned manner was measured in the samemanner as described above.

The sum a of the respective abundance ratios of Co atoms and Al atoms inthe portion to a depth of 30 Å from the surface of each of the hydrogenabsorbing alloys was found, and the sum b of the respective abundanceratios of Co atoms and Al atoms in a bulk region inside the hydrogenabsorbing alloy was found, to calculate a/b in the same manner asdescribed above. The results were together shown in the following Table6.

TABLE 6 embod- embod- iment iment embodiment comparative 13 14 15example 12 treating conditions of acid solution pH 1.0 1.0 1.0 1.0liquid temperature 25 25 25 25 (° C.) anthraquinone (ppm) 50 50 50 50Al(OH)₃ (% by weight) 1 3 5 7 COCl₂ (% by weight) 1 3 5 7 abundanceratio of atoms on surface Co (atm/%) 20.03 21.08 3.54 9.99 Al (atm/%)2.78 3.23 3.44 2.56 a (atm/%) 22.81 24.31 6.98 2.55 abundance ratio ofatoms inside b (atm/%) 17.34 17.90 7.99 7.98 a/b 1.32 1.36 1.50 1.25

As a result, in the hydrogen absorbing alloys in the embodiments 13 to15, the value of a/b was not less than 1.30, which satisfied theconditions of the present invention. On the other hand, in the hydrogenabsorbing alloy in the comparative example 12 which was surface-treatedusing an acid solution to which 7% by weight, which is more than 5% byweight, of Al(OH)₃ and CoCl₂ were added, the value of a/b was less than1.30.

(Embodiments 16 to 18 and Comparative Example 13)

In the embodiments 16 to 18 and the comparative example 13, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the liquid temperature of the acid solution was set to25° C., and 50 ppm of anthraquinone was added to the acid solution as inthe embodiments 13 to 15 and the comparative example 12, and the amountsof Al(OH)₃ and CoCl₂ which were added to the acid solution in theembodiment 16 were made the same as those in the embodiment 13, theamounts in the embodiment 17 were made the same as those in theembodiment 14, the amounts in the embodiment 18 were made the same asthose in the embodiment 15, and the amounts in the comparative example13 were made the same as those in the comparative example 12 as shown inthe following Table 7, while the initial pH of the acid solution waschanged as shown in the same table, to respectively surface-treat thehydrogen absorbing alloys.

Even when the initial pH of the acid solution was changed as describedabove, the value of a/b was hardly changed, that is, the value in theembodiment 16 was approximately the same as that in the embodiment 13,the value in the embodiment 17 was approximately the same as that in theembodiment 14, the value in the embodiment 18 was approximately the sameas that in the embodiment 15, and the value in the comparative example13 was approximately the same as that in the comparative example 12.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 1 to 3 and thecomparative examples 1 and 2 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were together shown in thefollowing Table 7.

TABLE 7 Al(OH)₃ + internal pressure characteristics COCl₂ (min) (% by pHweight) 0.5 0.7 1.0 1.5 2.0 3.0 embodiment 1 + 1 110 140 145 140 135 10516 embodiment 3 + 3 115 145 150 145 140 100 17 embodiment 5 + 5 115 145145 145 135 100 18 comparative 7 + 7 100 125 125 120 115 100 example 13

As apparent from the results, when the initial pH of the acid solutionwas changed, the charging time period indicating the internal pressurecharacteristics of the battery in each of the embodiments 16 to 18 inwhich the value of a/b was not less than 1.30 was longer than that inthe comparative example 13 in which the value of a/b was less than 1.30.Therefore, the emission of gas in the early stages was restrained, sothat a sufficient discharge capacity was obtained from the early stages.

In surface-treating the hydrogen absorbing alloy in the acid solution asdescribed above, when the hydrogen absorbing alloy was treated in anacid solution whose internal pH was in the range of 0.7 to 2.0, theinternal pressure characteristics of the nickel-hydrogen secondarybattery were further improved.

(Embodiments 19 to 21 and Comparative Example 14)

In the embodiments 19 to 21 and the comparative example 14, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the initial pH of the acid solution was set to 1.0,and 50 ppm of anthraquinone was added to the acid solution as in theembodiments 13 to 15 and the comparative example 12, and the amounts ofAl(OH)₃ and CoCl₂ which were added to the acid solution in theembodiment 19 were made the same as those in the embodiment 13, theamounts in the embodiment 20 were made the same as those in theembodiment 14, the amounts in the embodiment 21 were made the same asthose in the embodiment 15, and the amounts in the comparative example14 were made the same as those in the comparative example 12 as shown inthe following Table 8, while the liquid temperature of the acid solutionwas changed as shown in the same table, to respectively surface-treatthe hydrogen absorbing alloys.

Even when the liquid temperature of the acid solution was changed asdescribed above, the value of a/b was hardly changed, that is, the valuein the embodiment 19 was approximately the same as that in theembodiment 13, the value in the embodiment 20 was approximately the sameas that in the embodiment 14, the value in the embodiment 21 wasapproximately the same as that in the embodiment 15, and the value inthe comparative example 14 was approximately the same as that in thecomparative example 12.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 1 to 3 and thecomparative examples 1 and 2 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were together shown in thefollowing Table 8.

TABLE 8 internal pressure characteristics Al(OH)₃ + (min) CoCl₂ liquidtemperature of acid solution (% by (° C.) weight) 10.0 25.0 40.0 60.070.0 80.0 embodiment 1 + 1 120 145 140 145 140 105 19 embodiment 3 + 3135 150 150 145 145 110 20 embodiment 5 + 5 130 145 145 145 145 110 21comparative 7 + 7 120 125 135 135 110 105 example 14

As apparent from the results, when the liquid temperature of the acidsolution was set in the range of 25.0° C. to 70.0° C., the charging timeperiod indicating the internal pressure characteristics of the batteryin each of the embodiments 19 to 21 in which the value of a/b was notless than 1.30 as described above was longer than that in thecomparative example 14 in which the value of a/b was less than 1.30.Therefore, the emission of hydrogen gas in the early stages wasrestrained, so that a sufficient discharge capacity was obtained fromthe early stages.

(Embodiments 22 to 24 and Comparative Example 15)

In the embodiments 22 to 24 and the comparative example 15, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the initial pH of the acid solution was set to 1.0,and the liquid temperature thereof was set to 25° C. as in theembodiments 13 to 15 and the comparative example 12, and the amounts ofAl(OH)₃ and CoCl₂ which were added to the acid solution in theembodiment 22 were made the same as those in the embodiment 13, theamounts in the embodiment 23 were made the same as those in theembodiment 14, the amounts in the embodiment 24 were made the same asthose in the embodiment 15, and the amounts in the comparative example15 were made the same as those in the comparative example 12 as shown inthe following Table 9, while the amount of anthraquinone added to theacid solution was changed as shown in the same table, to respectivelysurface-treat the hydrogen absorbing alloys.

Even when the amount of anthraquinone added to the acid solution waschanged as described above, the value of a/b was hardly changed, thatis, the value in the embodiment 22 was approximately the same as that inthe embodiment 13, the value in the embodiment 23 was approximately thesame as that in the embodiment 14, the value in the embodiment 24 wasapproximately the same as that in the embodiment 15, and the value inthe comparative example 15 was approximately the same as that in thecomparative example 12.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 1 to 3 and thecomparative examples 1 and 2 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were together shown in thefollowing Table 9.

TABLE 9 internal pressure characteristics Al(OH)₃ + (min) CoCl₂ amountof added anthraquinone (% by (ppm) weight) 0.0 5.0 10.0 50.0 100.0 200.0embodiment 1 + 1 120 140 145 145 145 100 22 embodiment 3 + 3 125 145 150150 145 110 23 embodiment 5 + 5 120 145 145 145 145 100 24 comparative7 + 7 120 125 130 125 120 100 example 15

As apparent from the results, when the amount of anthraquinone added tothe acid solution was in the range of 5.0 ppm to 100.0 ppm, the chargingtime period indicating the internal pressure characteristics of the.battery in each of the embodiments 12 to 24 in which the value of a/bwas not less than 1.30 as described above was longer than that in thecomparative example 15 in which the value of a/b was less than 1.30.Therefore, the emission of hydrogen gas in the early stages wasrestrained, so that a sufficient discharge capacity was obtained fromthe early stages.

(Embodiments 25 to 27 and Comparative Examples 16 to 18)

In the embodiments 25 to 27 and the comparative examples 16 to 18,hydrogen absorbing alloy powder having a composition ofMmNi_(3.1)Co_(0.8)Al_(0.4)Mn_(0.7) was also used as described above.

The surface of the hydrogen absorbing alloy powder was treated in anacid solution using hydrochloric acid.

In thus treating the surface of the hydrogen absorbing alloy powder inthe acid solution, the initial pH of the acid solution was set to 1.0,and the liquid temperature thereof was set to 25° C., as shown in thefollowing Table 10. Further, in the embodiments 25 to 27 and thecomparative example 16, aluminum chloride (AlCl₃) was added as analuminum compound to the acid solution in a proportion as shown in thesame table, and 50 ppm of anthraquinone was added. In the comparativeexample 17, 50 ppm of only anthraquinone was added. In the comparativeexample 18, neither of aluminum chloride and anthraquinone was added.

A hydrogen absorbing alloy was immersed in each of the acid solutionsadjusted in the above-mentioned manner until the pH thereof would be7.0, to treat the surface of the hydrogen absorbing alloy.

The abundance ratio of each type of atoms in a portion to a depth of 30Å from the surface of each of the hydrogen absorbing alloyssurface-treated in the above-mentioned manner was then measured in theabove-mentioned manner.

The sum A of the respective abundance ratios of Co atoms, Al atoms andMn atoms in the portion to a depth of 30 Å from the surface of each ofthe hydrogen absorbing alloys was found in the same manner as describedabove, and the sum B of the respective abundance ratios of Co atoms, Alatoms and Mn atoms in a bulk region inside the hydrogen absorbing alloywas found, to calculate A/B. The results thereof were together shown inthe following Table 10.

TABLE 10 embodiment comparative example 25 26 27 16 17 18 treatingconditions of acid solution pH 1.0 1.0 1.0 1.0 1.0 1.0 liquidtemperature 25 25 25 25 25 25 (° C.) AlCl₃ (% by weight) 1 3 5 7 0 0anthraquinone (ppm) 50 50 50 50 50 0 abundance ratio of atoms on surfaceCo (atm/%) 19.87 20.98 22.12 19.23 15.56 15.56 Al (atm/%) 2.23 2.56 2.982.34 1.20 1.20 Mn (atm/%) 4.78 5.23 5.56 5.34 3.66 3.66 A (atm/%) 26.8828.77 30.66 26.91 20.42 20.42 abundance ratio of atoms inside B (atm/%)22.02 22.76 23.54 22.98 21.81 21.81 A/B 1.22 1.26 1.30 1.17 0.94 0.94

As a result, in the hydrogen absorbing alloys in the embodiments 25 to27, the value of A/B was not less than 1.20, which satisfied theconditions of the present invention. On the other hand, in the hydrogenabsorbing alloy in the comparative example 16 which was treated using anacid solution to which 7% by weight, which is more than 5% by weight, ofAlCl₃ was added, and the hydrogen absorbing alloy in each of thecomparative examples 17 and 18 which was treated using an acid solutionto which no AlCl₃ was added, the value of A/B was less than 1.20.

20 parts by weight of a 5% solution of polyethylene oxide which is abinder was added and mixed with 100 parts by weight of each of thehydrogen absorbing alloys surface-treated as shown in the embodiments 25to 27 and the comparative examples 16 and 17, and paste was prepared,was applied to both surfaces of a conductive substrate composed of apunched metal nickel-plated and was dried at room temperature, and wasthen cut to predetermined sizes, to fabricate each of hydrogen absorbingalloy electrodes in the embodiments 25 to 27 and the comparativeexamples 16 and 17.

Nickel-hydrogen secondary batteries were respectively fabricated in thesame manner as described in the embodiments 1 to 3 and the comparativeexamples 1 and 2 using the hydrogen absorbing alloy electrodes thusfabricated as their negative electrodes.

Each of the nickel-hydrogen secondary batteries fabricated in theabove-mentioned manner was charged at a charging current of 0.2 C forsix hours under room temperature (ordinary temperature), and was thendischarged at a discharging current of 0.2 C under low temperature of 0°C., to find the initial discharge capacity of the nickel-hydrogensecondary battery. The results thereof were shown in the following Table11.

TABLE 11 type of hydrogen absorbing initial discharge capacity alloyelectrode (mAh) embodiment 25 675 embodiment 26 677 embodiment 27 699comparative example 16 473 comparative example 17 445

As apparent from the results, in each of the nickel-hydrogen secondarybatteries using as their negative electrodes the hydrogen absorbingalloy electrodes in the embodiments 25 to 27 using the hydrogenabsorbing alloys in which the value of A/B was not less than 1.20, theinitial discharge capacity thereof under low temperature of 0° C. washigher, and the discharge characteristics thereof under low temperaturewere improved, as compared with those in each of the nickel-hydrogensecondary batteries using as their negative electrodes the hydrogenabsorbing alloy electrodes in the comparative examples 16 and 17respectively using the hydrogen absorbing alloys in which the value ofA/B was less than 1.20.

(Embodiments 28 to 30 and Comparative Examples 19 to 21)

In the embodiments 28 to 30 and the comparative examples 19 to 21, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the liquid temperature of the acid solution was set to25° C., and the amounts of AlCl₃ and anthraquinone which were added tothe acid solution in the embodiment 28 were made the same as those inthe embodiment 25, the amounts in the embodiment 29 were made the sameas those in the embodiment 26, the amounts in the embodiment 30 weremade the same as those in the embodiment 27, the amounts in thecomparative example 19 were made the same as those in the comparativeexample 16, the amounts in the comparative example 20 were made the sameas those in the comparative example 17, and the amount in thecomparative example 21 were made the same as those in the comparativeexample 18, while the initial pH of the acid solution was changed asshown in the same table, to respectively surface-treat the hydrogenabsorbing alloys.

Even when the initial pH of the acid solution was changed as describedabove, the value of A/B was hardly changed, that is, the value in theembodiment 28 was approximately the same as that in the embodiment 25,the value in the embodiment 29 was approximately the same as that in theembodiment 26, the value in the embodiment 30 was approximately the sameas that in the embodiment 27, the value in the comparative example 19was approximately the same as that in the comparative example 16, thevalue in the comparative example 20 was approximately the same as thatin the comparative example 17, and the value in the comparative example21 was approximately the same as that in the comparative example 18.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 25 to 27 and thecomparative examples 16 and 17 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure of each of the nickel-hydrogen secondary batteriesthus fabricated was measured while charging the battery at a current of1000 mA (1C) under room temperature, to find a charging time periodelapsed until the internal pressure of the battery reaches 10 kgf/cm².The charging time period was shown as the internal pressurecharacteristics in the early stages of the nickel-hydrogen secondarybattery in the following Table 12. In determining the internal pressurecharacteristics, tests were conducted with respect to fournickel-hydrogen secondary batteries, and the average value thereof wasshown.

TABLE 12 internal pressure AlCl₃ anthra- characteristics (min) (% byquinone pH weight) (ppm) 0.5 0.7 1.0 1.5 2.0 3.0 embodiment 1 50 100 135140 140 135 100 28 embodiment 3 50 100 135 145 145 135 100 29 embodiment5 50 100 145 145 145 135 100 30 comparative 7 50 95 125 120 120 110 90example 19 comparative o 50 95 115 120 120 110 90 example 20 comparative0 0 95 110 125 120 115 90 example 21

As apparent from the results, even when the initial pH of the acidsolution was changed, the charging time period indicating the internalpressure characteristics of the battery in each of the embodiments 28 to30 in which the value of A/B was not less than 1.20 as in theabove-mentioned embodiments 25 to 27 was longer than that in each of thecomparative examples 19 to 21 in which the value of A/B was less than1.20 as in the comparative examples 16 to 17. Therefore, the emission ofhydrogen gas in the early stages was restrained, so that a sufficientdischarge capacity was obtained from the early stages.

In surface-treating the hydrogen absorbing alloy in the acid solution asdescribed above, when the hydrogen absorbing alloy was treated in anacid solution whose initial pH was in the range of 0.7 to 2.0, theinternal pressure characteristics of each of the nickel-hydrogensecondary batteries were improved.

(Embodiments 31 to 33 and Comparative Examples 22 to 24)

In the embodiments 31 to 33 and the comparative examples 22 to 24, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the initial pH of the acid solution was set to 1.0,and the amounts of AlCl₃ and anthraquinone which were added to the acidsolution in the embodiment 31 were made the same as those in theembodiment 25, the amounts in the embodiment 32 were made the same asthose in the embodiment 26, the amounts in the embodiment 33 were madethe same as those in the embodiment 27, the amounts in the comparativeexample 22 were made the same as those in the comparative example 16,the amounts in the comparative example 23 were made the same as those inthe comparative example 17, and the amounts in the comparative example24 were made the same as those in the comparative example 18 as shown inthe following Table 13, while the liquid temperature of the acidsolution was changed as shown in the same table, to respectivelysurface-treat the hydrogen absorbing alloys.

Even when the liquid temperature of the acid solution was changed asdescribed above, the value of A/B was hardly changed, that is, the valuein the embodiment 31 was approximately the same as that in theembodiment 25, the value in the embodiment 32 was approximately the sameas that in the embodiment 26, the value in the embodiment 33 wasapproximately the same as that in the embodiment 27, the value in thecomparative example 22 was approximately the same as that in thecomparative example 16, the value in the comparative example 23 wasapproximately the same as that in the comparative example 17, and thevalue in the comparative example 24 was approximately the same as thatin the comparative example 18.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 25 to 27 and thecomparative examples 16 and 17 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybatteries were respectively fabricated using the hydrogen absorbingalloy electrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were shown in the following Table13.

TABLE 13 internal pressure characteristics (min) AlCl₃ anthra- liquidtemperature of acid (% by quinone solution (° C.) weight) (ppm) 10.025.0 40.0 60.0 70.0 80.0 embodiment 1 50 120 140 140 145 135 95 31embodiment 3 50 120 145 145 145 140 95 32 embodiment 5 50 120 145 145145 145 95 33 comparative 7 50 120 120 135 130 110 100 example 22comparative 0 59 115 120 120 120 110 90 example 23 comparative 0 0 120125 120 120 110 100 example 24

As apparent from the results, when the liquid temperature of the acidsolution was set in the range of 25.0° C. to 70.0° C., the charging timeperiod indicating the internal pressure characteristics of the batteryin each of the embodiments 31 to 33 in which the value of A/B was notless than 1.20 as described above was longer than that in each of thecomparative examples 22 to 24 in which the value of A/B was less than1.20. Therefore, the emission of gas in the early stages was restrained,so that a sufficient discharge capacity was obtained from the earlystages.

(Embodiments 34 to 36 and Comparative Examples 25 and 26)

In the embodiments 34 to 36 and the comparative examples 25 to 26, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the initial pH of the acid solution was set to 1.0,the liquid temperature thereof was set to 25° C., and the amount ofAlCl₃ added to the acid solution in the embodiment 34 was made the sameas that in the embodiment 25, the amount in the embodiment 35 was madethe same as that in the embodiment 26, the amount in the embodiment 37was made the same as that in the embodiment 27, the amount in thecomparative example 25 was made the same as that in the comparativeexample 16, and the amount in the comparative example 26 was made thesame as that in the comparative example 17 as shown in the followingTable 14, while the amount of anthraquninone added to the acid solutionwas changed as shown in the same table, to respectively surface-treatthe hydrogen absorbing alloys.

Even when the amount of anthraquinnone added to the acid solution waschanged as described above, the value of A/B was hardly changed, thatis, the value in the embodiment 34 was approximately the same as that inthe embodiment 25, the value in the embodiment 35 was approximately thesame as that in the embodiment 26, the value in the embodiment 36 wasapproximately the same as that in the embodiment 27, the value in thecomparative example 25 was approximately the same as that in thecomparative example 16, and the value in the comparative example 26 wasapproximately the same as that in the comparative example 17.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 25 to 27 and thecomparative examples 16 and 17 using the hydrogen absorbing alloysobtained in the above-mentioned manner, and nickel-hydrogen secondarybattery were respectively fabricated using the hydrogen absorbing alloyelectrodes as their negative electrodes.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were shown in the following Table14.

TABLE 14 internal pressure characteristics (min) AlCl₃ amount of addedanthraquinone (% by (ppm) weight) 0.0 5.0 10.0 50.0 100.0 200.0embodiment 1 125 140 140 140 135 95 34 embodiment 3 125 14& 145 145 14095 35 embodiment 5 130 145 145 145 145 95 36 comparative 7 125 130 130120 120 100 example 25 comparative 0 125 110 120 120 90 80 example 26

As apparent from the results, when the amount of anthraquinone added tothe acid solution was in the range of 5.0 ppm to 100.0 ppm, the chargingtime period indicating the internal pressure characteristics of thebattery in each of the embodiments 34 to 36 in which the value of A/Bwas not less than 1.20 as described above was longer than that in eachof the comparative examples 25 and 26 in which the value of A/B was lessthan 1.20. Therefore, the emission of hydrogen gas in the early stageswas restrained, so that a sufficient discharge capacity was obtainedfrom the early stages.

(Embodiments 37 to 39 and Comparative Example 27)

In the embodiments 37 to 39 and the comparative example 27, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the initial pH of the acid solution was set to 1.0,and the liquid temperature thereof was set to 25° C. as in theembodiments 25 to 27 and the comparative examples 16 to 18, and 50 ppmof anthraquinone was added, while aluminum hydroxide Al(OH)₃ was addedas an aluminum compound to the acid solution in a proportion as shown inthe following Table 15.

The abundance ratio of each type of atoms in a portion to a depth of 30Å from the surface of each of the hydrogen absorbing alloyssurface-treated in the above-mentioned manner was measured in theabove-mentioned manner.

The sum A of the respective abundance ratios of Co atoms, Al atoms andMn atoms in the portion to a depth of 30 Å from the surface of each ofthe hydrogen absorbing alloys was found, and the sum B of the respectiveabundance ratios of Co atoms, Al atoms and Mn atoms in a bulk regioninside the hydrogen absorbing alloy was found, to calculate A/B in thesame manner as described above. The results thereof were together shownin the following

TABLE 15 embod- embod- iment iment embodiment comparative 37 38 39example 27 treating conditions of acid solution pH 1.0 1.0 1.0 1.0liquid temperature 25 25 25 25 (° C.) anthraquinone (ppm) 50 50 50 50Al(OH)₃ (% by weight) 1 3 5 7 abundance ratio of atoms on surface Co(atm/%) 20.10 21.02 23.09 20.09 Al (atm/%) 2.43 2.66 3.01 2.34 Mn(atm/%) 4.88 5.32 6.01 3.76 A (atm/%) 27.41 29.00 32.11 26.19 abundanceratio of atoms inside B (atm/%) 22.30 22.90 23.46 22.09 A/B 1.23 1.271.37 1.19

As a result, in the hydrogen absorbing alloys in the embodiments 37 to39, the value of A/B was not less than 1.20, which satisfied theconditions of the present invention. On the other hand, in the hydrogenabsorbing alloy in the comparative example 27 which was treated using anacid solution to which 7% by weight, which is more than 5% by weight, ofAl(OH)₃ was added, the value of A/B was less than 1.20.

(Embodiments 40 to 42 and Comparative Example 28)

In the embodiments 40 to 42 and the comparative example 28, insurface-treating in an acid solution the above-mentioned hydrogenabsorbing alloys, the liquid temperature of the acid solution was set to25° C., and 50 ppm of anthraquinone was added to the acid solution as inthe embodiments 37 to 39 and the comparative example 27, and the amountof aluminum hydroxide Al(OH)₃ added to the acid solution in theembodiment 40 was made the same as that in the embodiment 37, the amountin the embodiment 41 was made the same as that in the embodiment 38, theamount in the embodiment 42 was made the same as that in the embodiment39, and the amount in the comparative example 28 was made the same asthat in the comparative example 27 as shown in the following Table 16,while the initial pH of the acid solution was changed as shown in thesame table, to respectively surface-treat the hydrogen absorbing alloys.

Even when the initial pH of the acid solution was changed as describedabove, the value of A/B was hardly changed, that is, the value in theembodiment 40 was approximately the same as that in the embodiment 37,the value in the embodiment 41 was approximately the same as that in theembodiment 38, the value in the embodiment 42 was approximately the sameas that in the embodiment 39, and the value in the comparative example28 was approximately the same as that in the comparative example 27.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 25 to 27 and thecomparative examples 16 and 17 using the hydrogen absorbing alloysobtained in the above-mentioned manner.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were shown in the following Table16.

TABLE 16 internal pressure characteristics Al(OH)₃ (min) (% by pHweight) 0.5 0.7 1.0 1.5 2.0 3.0 embodiment 1 95 135 135 140 135 95 40embodiment 3 100 140 140 140 140 100 41 embodiment 5 100 145 145 145 13595 42 comparative 7 95 120 125 125 110 90 example 28

As apparent from the results, when the initial pH of the acid solutionwas changed, the charging time period indicating the internal pressurecharacteristics of the battery in each of the embodiments 40 to 42 inwhich the value of A/B was not less than 1.20 was longer than that inthe comparative example 28 in which the value of A/B was less than 1.20.Therefore, the emission of hydrogen gas in the early stages wasrestrained, so that a sufficient discharge capacity was obtained fromthe early stages.

In surface-treating the hydrogen absorbing alloy in the acid solution asdescribed above, when the hydrogen absorbing alloy was treated in theacid solution whose initial pH was in the range of 0.7 to 2.0, theinternal pressure characteristics of each of the nickel-hydrogensecondary batteries were further improved.

(Embodiments 43 to 45 and Comparative Example 29)

In the embodiments 43 to 45 and the comparative example 29, insurface-treating in an acid solution hydrogen absorbing alloys, theinitial pH of the acid solution was set to 1.0, and 50 ppm ofanthraquinone was added to the acid solution as in the embodiments 37 to39 and the comparative example 27, and the amount of Al(OH)₃ added tothe acid solution in the embodiment 43 was made the same as that in theembodiment 37, the amount in the embodiment 44 was made the same as thatin the embodiment 28, the amount in the embodiment 45 was made the sameas that in the embodiment 29, and the amount in the comparative example29 was made the same as that in the comparative example 27 as shown inthe following Table 17, while the liquid temperature of the acidsolution was changed as shown in the same table, to respectivelysurface-treat the hydrogen absorbing alloys.

Even when the liquid temperature of the acid solution was changed asdescribed above, the value of A/B was hardly changed, that is, the valuein the embodiment 43 was approximately the same as that in theembodiment 37, the value in the embodiment 44 was approximately the sameas that in the embodiment 38, the value in the embodiment 45 wasapproximately the same as that in the embodiment 39, and the value inthe comparative example 29 was approximately the same as that in thecomparative example 27.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 25 to 27 and thecomparative examples 16 and 17 using the hydrogen absorbing alloysobtained in the above-mentioned manner.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were shown in the following Table17.

TABLE 17 internal pressure characteristics (min) Al(OH)₃ liquidtemperature of acid solution (% by (° C.) weight) 10.0 25.0 40.0 60.070.0 80.0 embodiment 1 120 135 145 145 140 95 43 embodiment 3 120 140145 145 140 95 44 embodiment 5 120 145 145 145 145 95 45 comparative 7120 125 125 130 115 95 example 29

As apparent from the results, when the liquid temperature of the acidsolution was set in the range of 25.0° C. to 70.0° C., the charging timeperiod indicating the internal pressure characteristics of the batteryin each of the embodiments 43 to 45 in which the value of A/B was notless than 1.20 as described above was longer than that in thecomparative example 29 in which the value of A/B was less than 1.20.Therefore, the emission of hydrogen gas in the early stages wasrestrained, so that a sufficient discharge capacity was obtained fromthe early stages.

(Embodiments 46 to 48 and Comparative Example 30)

In the embodiments 46 to 48 and the comparative example 30, insurface-treating in an acid solution hydrogen absorbing alloys, theinitial pH of the acid solution was set to 1.0, the liquid temperaturethereof was set to 25° C. as in the embodiments 37 to 39 and thecomparative example 27, and the amount of aluminum hydroxide Al(OH)₃added to the acid solution in the embodiment 46 was made the same asthat in the embodiment 37, the amount in the embodiment 47 was made thesame as that in the embodiment 38, the amount in the embodiment 49 wasmade the same as that in the embodiment 39, and the amount in thecomparative example 30 was made the same as that in the comparativeexample 27 as shown in the following Table 18, while the amount ofanthraquinone added to the acid solution was changed as shown in thesame table, to respectively surface-treat the hydrogen absorbing alloys.

Even when the amount of anthraquinone added to the acid solution waschanged as described above, the value of A/B was hardly changed, thatis, the value in the embodiment 46 was approximately the same as that inthe embodiment 37, the value in the embodiment 47 was approximately thesame as that in the embodiment 38, the value in the embodiment 48 wasapproximately the same as that in the embodiment 39, and the value inthe comparative example 30 was approximately the same as that in thecomparative example 27.

Hydrogen absorbing alloy electrodes were then respectively fabricated inthe same manner as described in the embodiments 25 to 27 and thecomparative examples 16 and 17 using the hydrogen absorbing alloysobtained in the above-mentioned manner.

The internal pressure in the early stages of each of the nickel-hydrogensecondary batteries thus fabricated was measured in the same manner asdescribed above. The results thereof were shown in the following Table18.

TABLE 18 internal pressure characteristics (min) Al(OH)₃ amount of addedanthraquinone (% by (ppm) weight) 0 5 10 50 100 200 embodiment 1 125 140140 135 135 95 46 embodiment 3 125 145 145 140 140 95 47 embodiment 5130 145 145 145 145 95 48 comparative 7 125 130 130 125 125 95 example30

As apparent from the results, when the amount of anthraquinone added tothe acid solution was in the range of 5 ppm to 100 ppm, the chargingtime period indicating the internal pressure characteristics of thebattery in each of the embodiments 46 to 48 in which the value of A/Bwas not less than 1.20 as described above was longer than that in thecomparative example 30 in which the value of A/B was less than 1.20.Therefore, the emission of hydrogen gas in the early stages wasrestrained, so that a sufficient discharge capacity was obtained fromthe early stages.

Although the present invention has been fully described by way ofexamples, it is to be noted that various changes and modification willbe apparent to those skilled in the art.

Therefore, unless otherwise such changes and modifications depart fromthe scope of the present invention, they should be construed as beingincluded therein.

What is claimed is:
 1. A hydrogen absorbing alloy electrode using ahydrogen absorbing alloy containing at least nickel, cobalt andaluminum, wherein letting a be the sum of the respective abundanceratios of cobalt atoms and aluminum atoms in a portion to a depth of 30Å from the surface of the hydrogen absorbing alloy, and b be the sum ofthe respective abundance ratios of cobalt atoms and aluminum atoms in abulk region inside the hydrogen absorbing alloy, conditions of a/b≧1.30are satisfied.
 2. A hydrogen absorbing alloy electrode using a hydrogenabsorbing alloy containing at least nickel, cobalt, aluminum andmanganese, wherein letting A be the sum of the respective abundanceratios of cobalt atoms, aluminum atoms and manganese atoms in a portionto a depth of 30 Å from the surface of the hydrogen absorbing alloy, andB be the sum of the respective abundance ratios of cobalt atoms,aluminum atoms and manganese atoms in a bulk region inside the hydrogenabsorbing alloy, conditions of A/B≧1.20 are satisfied.
 3. An alkalisecondary battery using a hydrogen absorbing alloy electrode containinga hydrogen absorbing alloy as its negative electrode, wherein saidhydrogen absorbing alloy contains at least nickel, cobalt and aluminum,and letting a be the sum of the respective abundance ratios of cobaltatoms and aluminum atoms in a portion to a depth of 30 Å from thesurface of the hydrogen absorbing alloy, and b be the sum of therespective abundance ratios of cobalt atoms and aluminum atoms in a bulkregion inside the hydrogen absorbing alloy, conditions of a/b≧1.30 aresatisfied.
 4. An alkali secondary battery using a hydrogen absorbingalloy electrode containing a hydrogen absorbing alloy at its negativeelectrode, wherein said hydrogen absorbing alloy contains at leastnickel, cobalt, aluminum and manganese, and letting A be the sum of therespective abundance ratios of cobalt atoms, aluminum atoms andmanganese atoms in a portion to a depth of 30 Å from the surface of thehydrogen absorbing alloy, and B be the sum of the respective abundanceratios of cobalt atoms, aluminum atoms and manganese atoms in a bulkregion inside the hydrogen absorbing alloy, conditions of A/B≧1.20 aresatisfied.